KR101342024B1 - Coating-type underlayer film forming composition containing naphthalene resin derivative for lithography - Google Patents

Abstract

It is providing the coating type underlayer film forming composition for lithography containing a naphthalene resin derivative.

General formula (1) below:

[Formula 1]

(Wherein A represents an organic group having an aromatic group, R ₁ represents a hydroxyl group, an alkyl group, an alkoxy group, a halogen group, a thiol group, an amino group, or an amide group, and m 1 represents the number of A substituted with a naphthalene ring) An integer of 6 is represented, m2 is an integer of 0 to 5 in terms of the number of R ₁ substituted with a naphthalene ring, and m1 + m2 is an integer of 1 to 6, and the balance in the case other than 6 represents a hydrogen atom. It is a coating type underlayer film forming composition for lithography containing the compound shown by ().

Naphthalene resin, lithography, underlayer, photoresist

Description

Coating type underlayer film-forming composition for lithography containing a naphthalene resin derivative {COATING-TYPE UNDERLAYER FILM FORMING COMPOSITION CONTAINING NAPHTHALENE RESIN DERIVATIVE FOR LITHOGRAPHY}

TECHNICAL FIELD This invention relates to the coating type underlayer film forming composition for lithography effective at the time of a semiconductor substrate process, and the photoresist pattern formation method using this coating type underlayer film forming composition.

BACKGROUND ART Conventionally, in semiconductor device manufacturing, fine processing by lithography using a photoresist composition has been performed. The fine processing is a photoresist pattern obtained by forming a thin film of a photoresist composition on a substrate to be processed such as a silicon wafer, irradiating active light such as ultraviolet rays through a mask pattern on which a pattern of a semiconductor device is drawn thereon, and developing the photoresist pattern. It is a processing method which etches a processed board | substrate, such as a silicon wafer, using as a protective film. However, in recent years, high integration of semiconductor devices has progressed, and active light rays used tend to be shortened from an KrF excimer laser (248 nm) to an ArF excimer laser (193 nm). As a result, the influence of diffuse reflection and standing waves from the active light substrate was a big problem. Therefore, a method of preparing a bottom anti-reflective coating (BARC) between the photoresist and the substrate to be processed has been widely studied.

As the antireflection film, inorganic antireflection films such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon, and an organic antireflection film made of a light absorbing material and a high molecular compound are known. While the former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, a sputtering apparatus, etc. for film formation, the latter is advantageous in that it does not require a special apparatus, and many studies have been made. For example, the novolak-type antireflection film and acrylic resin antireflection film which have a hydroxyl group and a light absorber which are a crosslinking reactor in the same molecule are mentioned (for example, refer patent document 1, patent document 2).

Preferable physical properties of the organic antireflection film material include a high absorbance against light or radiation, and no intermixing with the layer applied on the antireflection film (insoluble in the solvent used for the material applied on the antireflection film). And low molecular diffusion from the antireflection film material to the top coat resist during application or heat drying, and have a greater dry etching rate than the photoresist (for example, Non Patent Literature 1, See Non-Patent Document 2 and Non-Patent Document 3.).

Subsequently, when the resist pattern becomes finer, a problem of resolution or a problem that the resist pattern collapses after development occurs, and a thin film of the photoresist is required. For this reason, it is difficult to obtain a resist pattern film thickness sufficient for substrate processing, and not only a resist pattern but also the process of having a function as a mask at the time of processing a board | substrate also in the coating type underlayer film created between a resist and the semiconductor substrate to process are needed. Was done. As a coating type underlayer film for such a process, unlike a conventional high etchable coating type underlayer film, a coating type underlayer film for lithography having a selectivity of a dry etching rate close to the photoresist, which is smaller than the photoresist, The coating type underlayer film for lithography which has a small ratio of the selection rate of a dry etching rate compared with a semiconductor type substrate for lithography which has a selectivity of an etching rate, etc. (for example, nonpatent literature 4, nonpatent literature 5) Reference.). In addition, the anti-reflective performance can be imparted to such a coating-type underlayer film, and it can have the function of the conventional antireflection film together.

On the other hand, in order to obtain a fine resist pattern, the process of making a resist pattern and a coating type underlayer film thinner than the pattern width at the time of photoresist development at the time of application type underlayer film dry etching began to be used. As a coating type underlayer film for such a process, unlike a conventional high etch rate antireflection film, a coating type underlayer film having a selectivity of a dry etching rate close to a photoresist is required. Moreover, an antireflection film can also be provided to such a coating type underlayer film, and it can have the function of the conventional antireflection film together.

Patent Document 1: U.S. Patent No. 5919599

Patent Document 2: United States Patent No. 5693691 Specification

[Non-Patent Document 1] Tom Lynch, et al., [Properties and Performance of Near UV Reflectivity Control Layers], (United States), In Advance In resist In Advances in Resist Technology and Processing XI, Omkaram Nalamasu, Proceedings of SPIE, 1994, Vol. 2195, Vol. 2195, 225-. P. 229

[Non-Patent Document 2] G. Taylor, et al., 13, [Methacrylate Resist and Antireflective Coatings for 193 nm Lithography, USA], In Microlithography 1999: Advance in Resist Technology and Processing XVI, Will Conley, Proceeding of SPIE, 1999, Vol. 378 (Vol. 3678) ), Pp. 174-185

[Non-Patent Document 3] Jim D. Meador, et al., 6 [Recent Progress in 193nm Antireflective Coatings], (US), In Microlithography 1999: Ad Burns In Resist Technology and Processing XVI (Advances in Resist Technology and Processing XVI), Will Conley, Proceeding of SPIE, 1999, Vol. 3678 (Vol. 3678) , 800-809

Non-Patent Document 4: Tadayoshi Kokubo, [A Two-Layer Resist System: For Solving the Problems of Process Integration], (Japan), MNC2002 Technical Seminar, Forefront of the Resist Process, 2002, pp. 29-42

[Non-Patent Document 5] Yoshio Kawa, [High-Resolution, Posi- tive Chemically Amplified Two-Layer Resist], (Japan), MNC2002 Technical Seminar, Forefront of the Resist Process, 2002, pp. 43-48

This invention provides the coating type underlayer film forming composition for using for the lithographic process of semiconductor device manufacture. In addition, the present invention does not occur intermixing with the photoresist layer, obtains an excellent photoresist pattern, and has a small dryness compared to an application type underlayer film for lithography and a photoresist having a selectivity of a dry etching rate close to the photoresist. A coating type underlayer film for lithography having a selectivity of an etching rate and a coating type underlayer film for lithography having a selectivity of a dry etching rate smaller than that of a semiconductor substrate are provided. Moreover, this invention can also give the performance which absorbs the reflected light from a board | substrate effectively, when irradiation light of wavelengths, such as 248 nm, 193 nm, 157 nm, is used for microfabrication. Furthermore, an object of this invention is to provide the formation method of the photoresist pattern using this coating type underlayer film forming composition.

In view of such a phenomenon, the present inventors have intensively studied, and as a result, by using a naphthalene resin derivative having a naphthalene derivative in the main chain, an application-type underlayer film for photolithography and a photoresist having a selectivity of a dry etching rate close to the photoresist It has been found that a coating type underlayer film for lithography having a selectivity of a small dry etching rate compared with that of a semiconductor or a coating type underlayer film for lithography having a selectivity of a small dry etching rate relative to a semiconductor substrate can be formed, and further, functions as an antireflection film. The inventors also found that the refractive index n value and the attenuation coefficient k value at 248 nm, 193 nm, and 157 nm of the provision and the composition therefor can be controlled, thereby completing the present invention.

The present invention is, in a first aspect, the following general formula (1)

[Formula 1]

(Wherein A represents an organic group having an aromatic group, R ₁ represents a hydroxyl group, an alkyl group, an alkoxy group, a halogen group, a thiol group, an amino group, or an amide group, and m 1 represents the number of A substituted with a naphthalene ring) An integer of 6 is represented, m2 is an integer of 0 to 5 in terms of the number of R ₁ substituted with a naphthalene ring, and m1 + m2 is an integer of 1 to 6, and the balance in the case other than 6 represents a hydrogen atom. The coating type underlayer film forming composition for lithography containing the compound represented by ().

In a second aspect, the following general formula (2)

(2)

In the formula, A, R ₁ , m ₁ , m 2 and n have the same meanings as in Formula (1), and Ar ₁ is a substituted or unsubstituted aromatic group. Forming composition,

In a third aspect, the following general formula (3)

(3)

(Wherein X represents a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, a divalent hydrocarbon group having an ether bond having 2 to 10 carbon atoms, or a carbonyl group, and Z represents -O-,- Represents a linking group represented by OC (= 0)-, Ar ₂ represents an unsubstituted or aromatic ring substituted with a carboxylic acid, a carboxylic acid ester group, a hydroxyl group, an alkyl group, an alkoxy group, a sulfonic acid group, or a halogen group, and R ₁ , m1, m2 and n have the same meanings as in the formula (1).) A coating type underlayer film forming composition for lithography, comprising a compound represented by

In a fourth aspect, the following general formula (4)

[Formula 4]

(Wherein X and Z are the same as in formula (3), Ar ₁ is the same as in formula (2), Ar ₂ is the same as in formula (3), and R ₁ , m1, m2 and n have the same meanings as in the formula (1).) An application type underlayer film forming composition for lithography, comprising

In a fifth aspect, the following general formula (5)

[Chemical Formula 5]

Wherein X and Z are the same as in formula (3), Ar ₂ is the same as in formula (3), and R ₁ , m1, m2 and n are the meanings in formula (1) Coating type underlayer film-forming composition for lithography containing a compound represented by

In a sixth aspect, the coating type underlayer film forming composition for lithography according to any one of the first to fifth aspects, wherein the coating type underlayer film forming composition further comprises a crosslinkable compound,

In a seventh aspect, the coating type underlayer film forming composition for lithography according to any one of the first to fifth aspects, wherein the coating type underlayer film forming composition further includes an acid, an acid generator, or both.

In an eighth aspect, the coating type underlayer film forming composition for lithography according to the sixth aspect, wherein the coating type underlayer film forming composition further includes an acid, an acid generator, or both.

In a ninth aspect, a coating type underlayer film for lithography obtained by applying and baking the coating type underlayer film forming composition according to any one of the first to fifth aspects on a semiconductor substrate,

As a tenth viewpoint, the photoresist pattern used for semiconductor manufacture which includes the process of apply | coating and baking the coating type underlayer film forming composition in any one of a 1st viewpoint thru | or a 5th viewpoint on a semiconductor substrate, and forming a coating type underlayer film. Formation method,

From a 11th viewpoint, the process of forming this application | coating type underlayer film by the coating type underlayer film forming composition in any one of a 1st viewpoint thru | or a 5th viewpoint to a semiconductor substrate, the process of forming a resist film on it, exposure and image development A method of manufacturing a semiconductor device, including a step of forming a resist pattern, a step of etching the coating type underlayer film by the resist pattern, and a step of processing the semiconductor substrate by the patterned coating type underlayer film, and

From a 12th viewpoint, the process of forming this application | coating type underlayer film by the coating type underlayer film forming composition in any one of a 1st viewpoint thru | or a 5th viewpoint to a semiconductor substrate, the process of forming a hard mask on it, Furthermore, a resist on it A process of forming a film, a process of forming a resist pattern by exposure and development, a process of etching a hard mask by a resist pattern, a process of etching this application underlayer film by a patterned hard mask, and a patterned application underlayer It is a manufacturing method of a semiconductor device including the process of processing a semiconductor substrate with a film | membrane.

The coating type underlayer film forming composition of this invention contains any one or more of the naphthalene resin which has a unit structure represented by Formula (1), or the naphthalene resin which has a unit structure represented by Formula (2), and also contains a solvent. And the coating type underlayer film for lithography of this invention contains a crosslinking agent, a crosslinking catalyst, surfactant, etc. as an arbitrary component. The coating type underlayer film for lithography of this invention contains 0.1 to 70 weight%, Preferably it is 0.5 to 50 weight%, More preferably, it is 1 to 40 weight% in solid content except a solvent. The naphthalene derivative of formula (1) or the naphthalene resin of formula (2) is contained in solid content in the ratio of 5 to 100 weight%, Preferably it is 7 to 95 weight%, More preferably, it is 10 to 90 weight%.

The naphthalene resin which has a unit structure represented by Formula (1) or Formula (2) of this invention can also be used as a light absorbing compound at the time of patterning of a photoresist. The naphthalene resin of the present invention has a high absorption ability against light in the photosensitive characteristic wavelength region of the photosensitive component in the photoresist layer provided above the antireflection film, and is caused by standing waves generated by reflection from the substrate or by the step difference of the substrate surface. You can prevent diffuse reflection.

Naphthalene resin which has a unit structure represented by Formula (1) or Formula (2) is repeating unit n is 2-7000, or 2-5000, or 2-300 oligomer or polymer, The molecular weight is the coating solvent used Although it changes with solution viscosity, a film form, etc., it is 400-1 million, Preferably it is 500-50000, More preferably, it is 500-30000 in a weight average molecular weight.

The naphthalene resin which has a unit structure represented by Formula (1) or Formula (2) has a substituent (A). That is, the naphthalene novolak resin which has a side chain (A) which has an aromatic ring or a hetero aromatic ring at the terminal is shown. In addition, formula (1) may have a substituent (R ₁₎ consisting of a halogen group such as a hydroxyl group, an alkoxy group of carbon atoms, one alkyl group of 1 to 4, the number of 1 to 4 carbon atoms or a chlorine atom, a bromine atom, a naphthalene The number m1 of substituents A to the ring is 1 to 6, and the number m2 of substituents (R ₁ ) is 0 to 5, and the total number of substituents near the naphthalene ring of substituent A and substituent (R ₁ ) is m1 + m2 = 1. It is -6, and remainder in case other than 6 is a hydrogen atom.

Formula (3), which is a specific polymer of formula (1), has X in the substituent (A) moiety having a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, and an ether bond having 2 to 10 carbon atoms A divalent hydrocarbon group or a carbonyl group, Z represents a linking group represented by -O-, -OC (= O)-, Ar ₂ is unsubstituted or carboxylic acid, carboxylic acid ester group, hydroxyl group, alkyl group, alkoxy Aromatic ring (Ar ₂ ) substituted with a group, a sulfonic acid group, a halogen group, a thiol group, an amino group, or an amide group. Examples of this (Ar ₂ ) include heterocycles containing hetero atoms such as a benzene ring, a naphthalene ring, an anthracene ring, or a nitrogen atom thereof.

The unit of Formula (1) can further mention resin of Formula (2) which has a novolak structure of a naphthalene derivative and another aromatic compound. Another aromatic compound (Ar ₁ ) having a naphthalene derivative and a novolak structure in formula (2) is a derivative containing a hetero atom such as benzene, naphthalene, anthracene or a nitrogen atom thereof, or a carboxylic acid or carboxylic acid ester group And derivatives substituted with a hydroxyl group, an alkyl group, an alkoxy group, a sulfonic acid group, a halogen group, a thiol group, an amino group, or an amide group. Among these, a compound (Ar ₁₎ corresponds to a benzene of formula (5) is preferred.

The manufacturing method of Formula (1) and Formula (2) manufactures the naphthalene resin obtained by condensation-polymerizing naphthalene hydroxide and acetaldehyde, for example, makes epicrohydrin react with this naphthalene resin, and has a glycidyl ether group. This naphthalene resin can be manufactured and produced by reacting this naphthalene resin which has this glycidyl ether group, and the carboxylic acid and hydroxide of benzene, naphthalene, or anthracene.

Both terminals of the compounds of the formulas (1) and (2), the compounds of the formulas (3) to (5), and the exemplified compounds thereof may have a hydrogen atom or a hydroxyl group.

The said manufacturing method can use well-known manufacturing conditions. For example, the reaction conditions of novolak are by reacting for 4 to 72 hours at a temperature of 50 to 180 ° using a catalyst such as oxalic acid in a solvent or no solvent such as N-methylpyrrolidone. Reaction conditions of glycidyl etherification are made to react for 4 to 72 hours at a temperature of 50-180 degrees using catalysts, such as benzyl triethylammonium chloride, in solvents, such as a propylene glycol monomethyl ether, and also propylene glycol In a solvent such as monomethyl ether, the reaction is carried out at a temperature of 50 to 180 ° using a catalyst such as sodium hydroxide for 4 to 72 hours. The reaction conditions of the glycidyl ether group and the aromatic carboxylic acid and the hydroxide are reacted for 4 to 72 hours at a temperature of 50 to 180 ° using a catalyst such as benzyltriethylammonium chloride in a solvent such as propylene glycol monomethyl ether. By letting

It is not limited to this method, It can manufacture combining a well-known manufacturing method of the polymer which has novolak resin as a principal chain and has an aromatic substituent in a side chain.

It can represent with the following general formula as a specific example of the unit structure of naphthalene resin represented by Formula (1)-Formula (5).

In Formulas (6) to (157), the number n1 represents the number of substituents for the hydrogen atom of the aromatic ring, at least 1, and is the maximum number of hydrogen atoms present in the aromatic ring. Moreover, when there exist several n1 derived from another substituent in the same aromatic ring, each is at least 1, and the sum total is the number of hydrogen atoms which exist in an aromatic ring at maximum. n is the number of repeating units, and is the same as said Formula (1)-Formula (5).

The application type underlayer film forming composition for lithography of the present invention is preferably a crosslinked material by heating after application in the sense of preventing intermixing with a photoresist that coats the coating, and the coating type underlayer film forming composition for lithography of the present invention. Silver may further comprise a crosslinker component. As this crosslinking agent, a melamine type, a substituted element type, these polymer type, etc. are mentioned. Preferably it is a crosslinking agent which has at least 2 crosslinking substituents, It is methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylbenzoguanamine, butoxymethylbenzoguanamine, Methoxymethylurea, butoxymethylurea, methoxymethylthiourea, or methoxymethylthiourea. Condensers of these compounds may also be used. The amount of the crosslinking agent added varies depending on the coating solvent to be used, the substrate to be used, the required viscosity of the solution, the required film shape, and the like, but is preferably 0.001 to 80% by weight, preferably 0.01 to 50% by weight, based on the total solids. Preferably 0.05 to 40% by weight. Although these crosslinking agents may cause crosslinking reaction by self-condensation, when a crosslinkable substituent exists in the said high molecular compound of this invention, it can cause crosslinking reaction with these crosslinkable substituents.

In the present invention, as a catalyst for promoting the crosslinking reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, quenoic acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid and the like An acidic compound and / or thermal acid generators, such as 2,4,4,6- tetrabromocyclohexadienone, benzointosirate, 2-nitrobenzyl tosyrate, and other alkyl phosphonic acid alkyl ester, can be mix | blended. The compounding amount is 0.0001 to 20% by weight, preferably 0.0005 to 10% by weight based on the total solids.

In the coating type underlayer film forming composition for lithography of the present invention, a photoacid generator may be added in order to match the acidity with the photoresist coated on the upper layer in the lithography process. As a preferable photoacid generator, Onium salt type photoacid generators, such as bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate and a triphenylsulfonium trifluoromethanesulfonate, phenyl-bis ( Halogen-containing compound photoacid generators such as trichloromethyl) -s-triazine, sulfonic acid photoacid generators such as benzoin citrate and N-hydroxysuccinimide trifluoromethanesulfonate, and the like. The photoacid generator is 0.2 to 10% by weight, preferably 0.4 to 5% by weight based on the total solids.

As a coating type underlayer film material for lithography of the present invention, a light absorber, a rheology modifier, an adhesion aid, a surfactant, and the like may be further added, if necessary, in addition to the above.

As further light absorbers, for example, commercially available light absorbers described in [Technology and Market of Industrial Dyestuffs] (CMC Publishing) and [Dye Handbook] (Organic Synthetic Chemistry Association), for example CI Disperse Yellow 1, 3 , 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; C.I. Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; C.I. Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; C.I. Disperse Violet 43; C.I. Disperse Blue 96; C. I. Fluorescent Brightening Agents 112, 135, and 163; C. I. Solvent Orange 2 and 45; C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; C. I. Pigment Green 10; C. I. Pigment Brown 2 etc. can be used suitably. The said light absorber is normally mix | blended in the ratio of 10 weight% or less, Preferably it is 5 weight% or less with respect to the total solid of the coating type underlayer film material for lithography.

The rheology modifier is mainly added for the purpose of improving the fluidity of the coating type underlayer film forming composition, and in particular, improving the film thickness uniformity of the coating type underlayer film and filling properties of the coating type underlayer film forming composition in the hole in the baking step. do. Specific examples thereof include a phthalic acid derivative such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate, dinomal butyl adipate, diisobutyl adipate, and diisoocta. Adipic acid derivatives such as tiladipate and octyldecyl adipate, mulleinic acid derivatives such as dinomal butylmulate, diethylmulate and dinonylmulate, methyl oleate, butyl oleate and tetrahydrofurfuryl oleate And oleic acid derivatives or stearic acid derivatives such as normal butyl stearate and glyceryl stearate. These rheology modifiers are normally mix | blended in the ratio of less than 30 weight% with respect to the total solid of the coating type underlayer film material for lithography.

An adhesion aid is mainly added for the purpose of improving the adhesiveness of a board | substrate or photoresist and a coating type underlayer film forming composition, and especially preventing a photoresist from peeling in image development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxy. Silanes such as silane, diphenyldimethoxysilane and alkoxysilanes such as phenyltriethoxysilane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole and the like Silanes such as residual, vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, and indazole Heterocyclic compounds such as imidazole, 2-melcaptobenzimidazole, 2-melcaptobenzothiazole, 2-melcaptobenzoxazole, urazol, thiouracil, melcaptomidazole, and melcaptopyrimidine, 1,1-dimethylurea And urea such as 1,3-dimethylurea or thiourea compounds. These adhesion aids are mix | blended in the ratio of less than 5 weight% normally, Preferably it is less than 2 weight% with respect to the total solid of the coating type underlayer film material for lithography.

The coating type underlayer film material for lithography of the present invention can be blended with a surfactant in order to further improve applicability to surface unevenness without occurrence of pinholes or streaks. As surfactant, For example, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, Polyoxyethylene alkylallyl ethers such as polyoxyethylene nonyl phenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopulmitate, sorbitan monostearate, sorbitan monoolee Sorbitan fatty acid esters such as ate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopulmitate, polyoxyethylene sorbitan monostearate, polyoxy Polyoxyethylene, such as ethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate Nonionic surfactants, such as non-fatty acid ester, F-top EF301, EF303, EF352 (made by Tochem product), Megapak F171, F173 (made by Dainippon Inky Co., Ltd.), Florado FC430, FC431 (Sumitomo 3M Co., Ltd.), Asahigard AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) Fluorine type surfactant, organosiloxane polymer KP341 (Shin-Etsu) Kagaku Kogyo Co., Ltd.) etc. are mentioned. The compounding quantity of these surfactant is 0.2 weight% or less normally, Preferably it is 0.1 weight% or less with respect to the total solid of the coating type underlayer film material for lithography of this invention. These surfactants may be added alone or in combination of two or more kinds.

In the present invention, as the solvent for dissolving the above-mentioned high molecular compound, crosslinking agent component, crosslinking catalyst and the like, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl vertical solbu acetate, ethyl vertical solbu acetate, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydride Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxy acetate, methyl 2-hydroxy-3-methyl butyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate Ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, Ethyl lactate, butyl lactate, or the like can be used. These organic solvents are used individually or in combination of 2 or more types.

Furthermore, high boiling point solvents, such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate, can be mixed and used. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, and the like are preferable for improving the leveling property.

As the photoresist applied to the upper part of the coating type underlayer film for lithography in the present invention, both negative and positive types can be used, and a positive type photoresist composed of a novolak resin and 1,2-naphthoquinone diazide sulfonic acid ester, Chemically amplified photoresist consisting of a binder and a photoacid generator having a group which decomposes by an acid to increase the alkali dissolution rate, and a low molecular compound and a photoacid generator which decomposes with an alkali-soluble binder and an acid to increase the alkali dissolution rate of the photoresist. Chemically amplified photoresist, a chemically amplified photoresist consisting of a binder having a group which is decomposed by an acid to increase the alkali dissolution rate and a low molecular compound and a photoacid generator decomposed by an acid to increase the alkali dissolution rate of the photoresist Photoresist having Si atoms And, examples thereof include the Rohm and Haas Company, trade name: APEX-E.

As a developing solution of the photoresist which has a coating type underlayer film formed using the coating type underlayer film material for lithography of this invention, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethyl, 1st amines, such as amine and n-propylamine, 2nd amines, such as diethylamine and di-n-butylamine, 3rd amines, such as triethylamine and methyldiethylamine, dimethylethanolamine, triethanolamine, etc. Aqueous solutions of alkalis, such as quaternary ammonium salts, such as alcohol amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, cyclic amines, such as pyrrole and piperidine, can be used. Furthermore, alcohols, such as isopropyl alcohol, and surfactant, such as a nonionic type, can also be added and used for the said aqueous solution of alkalis. Among these, preferred developer solutions are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline.

Next, the photoresist pattern forming method of the present invention will be described. Spinners, coaters and the like on a substrate (for example, a transparent substrate such as a silicon / silicon dioxide film, a glass substrate, an ITO substrate, etc.) used in the manufacture of the precision integrated circuit device. After apply | coating a coating type underlayer film forming composition by the suitable coating method of, it bakes and hardens and creates a coating type underlayer film. As film thickness of a coating type underlayer film, 0.01-3.0 micrometers is preferable here. Moreover, as conditions for baking after application | coating, it is 1 to 120 minutes at 80-250 degreeC. Thereafter, one layer to several layers of coating material is formed directly on the coating type underlayer film or as necessary on the coating type underlayer film, and then a photoresist is applied, exposed through a predetermined mask, and developed, rinsed and dried. By doing so, a good photoresist pattern can be obtained. If necessary, post exposure bake (PEB) may be performed. Then, the coating type underlayer film of the portion where the photoresist is developed and removed by the above process can be removed by dry etching, and a desired pattern can be formed on the substrate.

That is, this coating type underlayer is formed by the process of forming this coating type underlayer film by a coating type underlayer film forming composition on a semiconductor substrate, the process of forming a resist film on it, the process of forming a resist pattern by exposure and image development, and a resist pattern. A semiconductor device can be manufactured through the process of etching a film, and the process of processing a semiconductor substrate with a patterned application | coating underlayer film.

Subsequently, as the resist pattern becomes finer, a problem of resolution or a problem that the resist pattern collapses after development occurs, and the thinning of the photoresist is required. For this reason, it is difficult to obtain a resist pattern film thickness sufficient for substrate processing, and the process which has not only a resist pattern but also the application | coating type underlayer film created between a resist and the semiconductor substrate to process has a function as a mask at the time of a substrate processing. . As a coating type underlayer film for such a process, unlike a conventional high-ethylate coating type underlayer film, the coating type underlayer film for lithography having a selectivity of the dry etching rate close to the photoresist and a small dry etching rate compared with the photoresist A coating-type underlayer film for lithography having a selectivity of lithography and a coating-type underlayer film for lithography having a selectivity of a small dry etching rate compared to a semiconductor substrate have been required. In addition, the coating type underlayer film may be provided with an antireflection performance, and may have a function of a conventional antireflection film.

On the other hand, in order to obtain a fine resist pattern, the process of making a resist pattern and a coating type underlayer film narrower than the pattern width at the time of photoresist development at the time of application type underlayer film dry etching also began to be used. As a coating type underlayer film for such a process, a coating type underlayer film having a selectivity of a dry etching rate close to the photoresist is required, unlike a conventional high ethylate antireflection film. In addition, the coating type underlayer film may be provided with an antireflection performance, and may have a function of a conventional antireflection film.

In the present invention, after depositing the coating type underlayer film of the present invention on a substrate, a film of one to several layers of coating film material is formed on the coating type underlayer film directly or as necessary on the coating type underlayer film, and then a photoresist is applied. It can be applied. As a result, the pattern width of the photoresist becomes narrow, and even when the photoresist is thinly coated in order to prevent the pattern from collapsing, substrate processing can be performed by selecting an appropriate etching gas.

That is, the process of forming this coating type underlayer film by a coating type underlayer film forming composition in a semiconductor substrate, the process of forming a hard mask by the coating film material containing a silicon component, etc. on it, Furthermore, the process of forming a resist film on it, A semiconductor substrate is formed by a process of forming a resist pattern by exposure and development, a process of etching a hard mask by a resist pattern, a process of etching this application underlayer film by a patterned hard mask, and a patterned application underlayer film. A semiconductor device can be manufactured through the process of processing the sigma.

The coating type underlayer film for lithography which consists of naphthalene resin of this invention has the characteristic which can obtain the suitable dry etching rate which satisfy | fills these requirements.

In the coating type underlayer film forming composition for lithography of the present invention, when the effect as an antireflection film is taken into consideration, the light absorbing portion is blown into the skeleton, so there is no diffusion into the photoresist during heat drying, and the light absorbing portion is sufficiently Since it has a large light absorption performance, the anti-reflective effect is high.

The coating type underlayer film forming composition for lithography of the present invention has high thermal stability, can prevent contamination of the upper layer film due to decomposition products during firing, and can afford a margin in the temperature margin of the firing step.

Furthermore, the coating type underlayer material for lithography of the present invention may be a material for preventing photoreflection and further preventing the interaction between the substrate and the photoresist, or a material or photoresist used for the photoresist, depending on the process conditions. It is possible to use the film as a film having a function of preventing adverse effects of the substance produced upon exposure to the substrate.

Hereinafter, although the Example and comparative example of this invention demonstrate more concretely, this invention is not limited by this.

Synthesis Example 1

50.0 g of the compound of formula (158) (manufactured by Daicel Kagaku Co., Ltd., product name: EHPE3150) and 57.4 g of 9-anthracenecarboxylic acid were dissolved in 435.7 g of propylene glycol monomethyl ether, and then 1.5 g of benzyltriethylammonium was dissolved. It was added, refluxed and reacted for 24 hours to obtain a polymer compound solution of formula (159). The GPC analysis of the obtained polymer compound showed a weight average molecular weight of 3000 in terms of standard polystyrene.

[Synthesis Example 2]

50.0 g of a compound of formula (160) (manufactured by Shinnitetsu Chemical Co., Ltd., product name: ESN175S) and 37.3 g of 9-anthracenecarboxylic acid were dissolved in 353.0 g of propylene glycol monomethyl ether, and then 1.0 g of benzyltriethylammonium was added. The mixture was refluxed and reacted for 24 hours to obtain a polymer compound solution of formula (161). As a result of GPC analysis of the obtained high molecular compound, the weight average molecular weight was 2500 in standard polystyrene conversion.

[Formula 160]

[Formula 161]

[Synthesis Example 3]

After dissolving 50.0 g of the compound of formula (162) (manufactured by Shinnitetsu Chemical Co., Ltd., product name: ESN375) and 60.1 g of 9-anthracenecarboxylic acid in 447.0 g of propylene glycol monomethyl ether, 1.6 g of benzyltriethylammonium was added. The mixture was refluxed and reacted for 24 hours to obtain a polymer compound solution of formula (163). As a result of GPC analysis of the obtained high molecular compound, the weight average molecular weight was 2500 in standard polystyrene conversion.

[Synthesis Example 4]

After dissolving 21 g of glycidyl methacrylate and 39 g of 2-hydroxypropyl methacrylate in 242 g of propylene glycol monomethyl ether, it heated up to 70 degreeC. Thereafter, 0.6 g of azobisisobutyronitrile was added while maintaining the reaction solution at 70 ° C, and reacted at 70 ° C for 24 hours to obtain a polymer compound solution of formula (164). The GPC analysis of the obtained high molecular compound showed a weight average molecular weight of 50000 in terms of standard polystyrene.

≪ EMI ID =

10 g of 9-anthracenecarboxylic acid and 0.3 g of benzyltriethylammonium chloride were added to 100 g of the solution having 20 g of the resin, and reacted at 130 ° C. for 24 hours to obtain a polymer compound solution of formula (165).

Formula 165

Synthesis Example 5

13.2 g of hydroxypropyl methacrylate and 6.8 g of benzyl methacrylate were dissolved in 74.4 g of tetrahydrofuran and then heated up to 70 ° C. Thereafter, 0.2 g of azobisisobutylonitrile was added while maintaining the reaction solution at 70 ° C, and reacted at 70 ° C for 24 hours. After cooling, the reaction solution was poured into diethyl ether, and the polymer was reprecipitated and dried under heat to obtain a resin of the formula (166). The GPC analysis of the obtained polymer compound showed a weight average molecular weight of 70000 in terms of standard polystyrene.

≪ EMI ID =

Example 1

To 10 g of propylene glycol monomethyl ether solution having 2 g of the polymer compound obtained in Synthesis Example 2, 0.4 g of tetrabutoxymethyl glycoluril and 0.05 g of pyridinium p-toluenesulfonic acid were mixed, 3.0 g of propylene glycol monomethyl ether and ethyl lactate. It dissolved in 11.0 g and used as a solution. Thereafter, the resultant was filtered using a polyethylene microfilter having a pore diameter of 0.10 µm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 µm to prepare a coating-type underlayer film solution for lithography.

[Example 2]

To 10 g of propylene glycol monomethyl ether solution having 2 g of the polymer compound obtained in Synthesis Example 3, 0.4 g of tetrabutoxymethyl glycoluril and 0.05 g of pyridinium p-toluenesulfonic acid were mixed, 3.0 g of propylene glycol monomethyl ether and ethyl lactate. It dissolved in 11.0 g and used as a solution. Thereafter, the resultant was filtered using a polyethylene microfilter having a pore diameter of 0.10 µm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 µm to prepare a coating-type underlayer film solution for lithography.

[Example 3]

0.4 g of tetrabutoxymethylglycoluril and 0.05 g of pyridinium p-toluenesulfonic acid in 5 g of a propylene glycol monomethyl ether solution having 1 g of the polymer compound obtained in Synthesis Example 1 and 5 g of a solution containing 1 g of the polymer compound obtained in Synthesis Example 2 Were mixed and dissolved in 3.0 g of propylene glycol monomethyl ether and 11.0 g of ethyl lactate to obtain a solution. Thereafter, the resultant was filtered using a polyethylene microfilter having a pore diameter of 0.10 µm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 µm to prepare a coating-type underlayer film solution for lithography.

Example 4

0.4 g of tetrabutoxymethylglycoluril and 2.5 g of pyridinium p-toluenesulfonic acid in 8 g of propylene glycol monomethyl ether solution having 1.6 g of the polymer compound obtained in Synthesis Example 1 and 2 g of solution having 0.4 g of the polymer compound obtained in Synthesis Example 2 0.05 g was mixed and dissolved in 3.0 g of propylene glycol monomethyl ether and 11.0 g of ethyl lactate to obtain a solution. Thereafter, the resultant was filtered using a polyethylene microfilter having a pore diameter of 0.10 µm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 µm to prepare a coating-type underlayer film solution for lithography.

Comparative Example 1

10 g of propylene glycol monomethyl ether solution having 2 g of the polymer compound obtained in Synthesis Example 4 was mixed with 0.5 g of tetramethoxymethyl glycoluril and 0.02 g of p-toluenesulfonic acid, and 37.3 g of propylene glycol monomethyl ether and propylene glycol monomethyl It was dissolved in 19.4 g of ether acetate to obtain a solution. Thereafter, the resultant was filtered using a polyethylene microfilter having a pore diameter of 0.10 µm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 µm to prepare an antireflection film solution.

Comparative Example 2

To 10 g of tetrahydrofuran solution containing 2 g of the polymer compound obtained in Synthesis Example 5, 0.5 g of hexamethoxymethylol melamine and 0.05 g of p-toluenesulfonic acid were mixed, and dissolved in 39.5 g of propylene glycol monomethyl ether to prepare a solution. Thereafter, the resultant was filtered using a polyethylene microfilter having a pore diameter of 0.10 µm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 µm to prepare an antireflection film solution.

(Measurement of optical parameters)

The coating type underlayer film solution prepared in Examples 1 to 4 and the antireflection film solution prepared in Comparative Examples 1 and 2 were applied onto a silicon wafer using a spinner. It heated at 205 degreeC for 1 minute on the hotplate, and formed the application | coating type underlayer film and the anti-reflective film (film thickness of 0.06 micrometer). And the refractive index (n value) and attenuation coefficient (k value) in these coating type underlayer film and antireflection film in wavelength 248nm and wavelength 193nm were measured using the spectroscopic ellipsometer. The results are shown in Table 1.

(Dissolution test for photoresist)

The coating type underlayer film solution prepared in Examples 1 to 4 and the antireflection film solution prepared in Comparative Examples 1 and 2 were applied onto a silicon wafer using a spinner. It heated at 205 degreeC for 1 minute on the hotplate, and formed the application | coating type underlayer film and the anti-reflective film (film thickness 0.10 micrometer). This coating type underlayer film and antireflection film were immersed in the solvent used for a resist, for example, ethyl lactate, and propylene glycol monomethyl ether, and it confirmed that it was insoluble in this solvent.

(Intermix Test with Photoresist)

The coating type underlayer film solution prepared in Examples 1 to 4 and the antireflection film solution prepared in Comparative Examples 1 and 2 were applied onto a silicon wafer using a spinner. It heated at 205 degreeC for 1 minute on the hotplate, and formed the application | coating type underlayer film and the anti-reflective film (film thickness 0.10 micrometer). A commercially available photoresist solution (manufactured by Cypress, trade name UV113, etc.) was applied to the upper layer of the coating underlayer film for lithography and the antireflection film by using a spinner. It heated at 120 degreeC for 1 minute on a hotplate, and post-exposure heating was performed at 115 degreeC for 1 minute after exposure of the photoresist. After the photoresist was developed, the film thicknesses of the coating type underlayer film and the antireflection film were measured, and the coating type underlayer film obtained from the coating type underlayer film solution prepared in Examples 1 to 4 and the antireflection film solution prepared in Comparative Examples 1 and 2 were used. And it was confirmed that intermixing of the antireflection film and the photoresist layer did not occur.

(Dry Etch Rate Measurement)

The coating type underlayer film solution prepared in Examples 1 to 4 and the antireflection film solution prepared in Comparative Examples 1 and 2 were applied onto a silicon wafer using a spinner. It heated at 205 degreeC for 1 minute on the hotplate, and formed the application | coating type underlayer film and the anti-reflective film (film thickness 0.10 micrometer). The dry etching rate was measured using a RIE system ES401 manufactured by Nihon Scientific Co., Ltd., a RIE-10NR manufactured by Samko, and TCP9400 manufactured by Lam Research.

In addition, similarly, the coating film was created on the silicon wafer using the spinner for the photoresist solution (made by Siflesa, brand name UV113). And dry etching rate was measured using the RIE system ES401 made from Nippon Scientific, and it compared with the dry etching rate of the application type underlayer film and antireflection film of Examples 1-4 and Comparative Examples 1 and 2. The results are shown in Table 1.

In addition, the dry etching rate of the semiconductor substrate was measured using a RIE-10NR manufactured by Samko and TCP9400 manufactured by Ram Research, and compared with the dry etching rates of the coating type underlayer film and the antireflection film of Examples 1 to 4 and Comparative Examples 1 and 2, respectively. . The results are shown in Table 2.

In Table 2, the measurement (1) of the coating-type underlayer film of the present invention, the dry etching rate of the non-resist (coating-type underlayer film / resist) is, was used CF ₄ gas as an etching gas.

Measurement (2) of the SiO ₂ film, the dry etching rate ratio (SiO ₂ / coating-type underlayer film) on the substrate for the coating-type underlayer film of the present invention, was used as an etching gas C ₄ F ₈ gas.

Measurement (3) of the silicon nitride film is dry-etching rate ratio (silicon nitride / coating-type underlayer film) on the substrate for the coating-type underlayer film of the present invention, was used for CHF ₃ gas as an etching gas.

Measuring (4) the dry-etching rate ratio (polysilicon / coating-type underlayer film) and the polysilicon film on the substrate for the coating-type underlayer film of the present invention, were used for Cl ₂ gas as the etching gas.

Refractive index n and optical extinction coefficient k Refractive index n
(Wavelength: 248 nm) Optical extinction coefficient k
(Wavelength: 248 nm) Refractive index n
(Wavelength 193nm) Optical extinction coefficient k
(Wavelength 193nm) Example 1 1.80 0.70 1.49 0.41 Example 2 1.62 0.87 1.54 0.32 Example 3 1.60 0.64 1.60 0.28 Example 4 1.48 0.68 1.61 0.21 Comparative Example 1 1.47 0.47 Comparative Example 2 1.82 0.34

Dry etching rate ratio Measure (One) (2) (3) (4) Example 1 0.9 6.2 5.1 3.7 Example 2 0.9 6.2 5.0 3.7 Example 3 1.0 7.0 4.5 3.1 Example 4 1.1 5.0 3.9 2.5 Comparative Example 1 1.3 3.7 2.8 2.0 Comparative Example 2 1.4 3.4 2.5 1.8

As a result, the coated underlayer film material for lithography of the present invention has a selectivity of a dry etching rate that is close to the photoresist or smaller than that of the photoresist, and a smaller dry etching than the semiconductor substrate, unlike the conventional high-ethylate antireflection film. It was found that it is possible to provide an excellent coating type underlayer film having a selectivity of speed and further having an effect as an antireflection film.

The present invention relates to a coating type underlayer film formed by using a resin containing a naphthalene derivative in a main chain and a coating type underlayer film forming composition for forming the coating type underlayer film.

By the coating type underlayer film forming composition of this invention, a favorable photoresist pattern shape can be formed, without intermixing with the upper layer part of a coating type underlayer film.

The coating type underlayer film forming composition of this invention can also be given the performance which suppresses reflection from a board | substrate efficiently, and can also have the effect as an antireflection film together.

By the coating type underlayer film forming composition of this invention, the outstanding application type which has a selection ratio of the dry etching rate near a photoresist, a selection ratio of the small dry etching rate compared with a photoresist, and a selection ratio of the small dry etching rate compared with a semiconductor substrate An underlayer film can be provided.

In order to prevent the resist pattern from collapsing after development as the resist pattern is miniaturized, the photoresist is thinned. In such a thin film resist, the resist pattern is transferred to the lower layer film by an etching process, the process of performing substrate processing using the lower layer film as a mask, or the resist pattern is transferred to the lower layer film by an etching process, and further transferred to the lower layer film. There exists a process of repeating the process of transferring a pattern to this underlayer film using a different gas composition, and finally performing substrate processing. The coating type underlayer film of this invention and its formation composition are effective for this process, and when processing a board | substrate using the coating type underlayer film of this invention, a processed substrate (for example, a thermal silicon oxide film, a silicon nitride film, Polysilicon film or the like).

On the other hand, in order to obtain a fine resist pattern, the process of making a resist pattern and a coating type underlayer film narrower than the pattern width at the time of photoresist image development also began to be used at the time of application type underlayer film dry etching. The coating type underlayer film of this invention and its formation composition are effective for this process, and have a selectivity of the dry etching rate close to a photoresist.

And the coating type underlayer film of this invention can be used as a film | membrane which has a anti-fouling film of a planarization film, a resist underlayer film, a photoresist layer, and dry etching selectivity. Thereby, the photoresist pattern formation in the lithography process of semiconductor manufacture can be performed easily and with high precision.

The present invention is free of intermixing with a photoresist layer, provides excellent photoresist patterns, and has a small dry etching compared to a photo-type underlayer film for lithography having a selectivity of a dry etching rate close to the photoresist and a photoresist. A coating type underlayer film for lithography having a selectivity of speed and a coating type underlayer film for lithography having a selectivity of a dry etching rate smaller than that of a semiconductor substrate are provided. Moreover, the coating type underlayer film material of this invention can give the effect which absorbs the reflected light from a board | substrate effectively when using irradiation light of wavelength 248 nm, 193 nm, 157 nm, etc. for microfabrication.

The coating type underlayer film forming composition of this invention can form an underlayer film easily by apply | coating an underlayer film forming composition on a board | substrate using a coating method, for example, a spinner, etc., and heating.

By using these properties, it can be applied to a process requiring a multilayer film for the manufacture of a semiconductor device requiring microfabrication with a small wiring width.

Claims (12)

General formula (1) below: [Formula 1]

(Wherein, A represents an organic group having an aromatic group, the aromatic group is a heterocyclic ring containing hetero atoms such as benzene ring, naphthalene ring, anthracene ring, or nitrogen atom thereof, R ₁ represents a hydroxyl group, an alkyl group, an alkoxy group, a halogen group, a thiol group, an amino group, or an amide group, m1 represents the integer of 1-6 by the number of A, m2 is an integer of 0 to 5 as the number of R ₁ , m1 + m2 is an integer of 1-6, the remainder in cases other than 6 represents a hydrogen atom, n represents a repeating unit of 2 to 7000.) Containing the compound represented by Coating type underlayer film forming composition for lithography. General formula (2) below: (2)

(Wherein, A represents an organic group having an aromatic group, the aromatic group is a heterocyclic ring containing hetero atoms such as benzene ring, naphthalene ring, anthracene ring, or nitrogen atom thereof, R ₁ represents a hydroxyl group, an alkyl group, an alkoxy group, a halogen group, a thiol group, an amino group, or an amide group, m1 represents the integer of 1-6 by the number of A, m2 is an integer of 0 to 5 as the number of R ₁ , m1 + m2 is an integer of 1-6, the remainder in cases other than 6 represents a hydrogen atom, n represents a repeating unit of 2 to 7000, Ar ₁ is an unsubstituted or aromatic group substituted with a carboxylic acid, a carboxylic acid ester group, a hydroxyl group, an alkyl group, an alkoxy group, a sulfonic acid group, a halogen group, a thiol group, an amino group, or an amide group.) Containing the compound represented by Coating type underlayer film forming composition for lithography. General formula (3) below: (3)

(Wherein, X represents a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, a divalent hydrocarbon group having an ether bond having 2 to 10 carbon atoms, or a carbonyl group, Z represents a linking group represented by -O-, -OC (= O)-, Ar ₂ represents an unsubstituted or aromatic ring substituted with a carboxylic acid, a carboxylic acid ester group, a hydroxyl group, an alkyl group, an alkoxy group, a sulfonic acid group, or a halogen group, and A represents an organic group having an aromatic group, the aromatic group is a heterocyclic ring containing hetero atoms such as benzene ring, naphthalene ring, anthracene ring, or nitrogen atom thereof, R ₁ represents a hydroxyl group, an alkyl group, an alkoxy group, a halogen group, a thiol group, an amino group, or an amide group, m1 represents the integer of 1-6 by the number of A, m2 is an integer of 0 to 5 as the number of R ₁ , m1 + m2 is an integer of 1-6, the remainder in cases other than 6 represents a hydrogen atom, n represents a repeating unit of 2 to 7000.) Containing the compound represented by Coating type underlayer film forming composition for lithography. General formula (4) below: [Formula 4]

(Wherein, X represents a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, a divalent hydrocarbon group having an ether bond having 2 to 10 carbon atoms, or a carbonyl group, Z represents a linking group represented by -O-, -OC (= O)-, Ar ₁ is an unsubstituted or aromatic group substituted with a carboxylic acid, a carboxylic acid ester group, a hydroxyl group, an alkyl group, an alkoxy group, a sulfonic acid group, a halogen group, a thiol group, an amino group, or an amide group, Ar ₂ represents an unsubstituted or aromatic ring substituted with a carboxylic acid, a carboxylic acid ester group, a hydroxyl group, an alkyl group, an alkoxy group, a sulfonic acid group, or a halogen group, and R ₁ represents a hydroxyl group, an alkyl group, an alkoxy group, a halogen group, a thiol group, an amino group, or an amide group, m1 represents the integer of 1-6 by the number of A, m2 is an integer of 0 to 5 as the number of R ₁ , m1 + m2 is an integer of 1-6, the remainder in cases other than 6 represents a hydrogen atom, n represents a repeating unit of 2 to 7000.) Containing the compound represented by Coating type underlayer film forming composition for lithography. General formula (5) [Chemical Formula 5]

(Wherein, X represents a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, a divalent hydrocarbon group having an ether bond having 2 to 10 carbon atoms, or a carbonyl group, Z represents a linking group represented by -O-, -OC (= O)-, Ar ₂ represents an unsubstituted or aromatic ring substituted with a carboxylic acid, a carboxylic acid ester group, a hydroxyl group, an alkyl group, an alkoxy group, a sulfonic acid group, or a halogen group, and R ₁ represents a hydroxyl group, an alkyl group, an alkoxy group, a halogen group, a thiol group, an amino group, or an amide group, m1 represents the integer of 1-6 by the number of A, m2 is an integer of 0 to 5 as the number of R ₁ , m1 + m2 is an integer of 1-6, the remainder in cases other than 6 represents a hydrogen atom, n represents a repeating unit of 2 to 7000.) Containing the compound represented by Coating type underlayer film forming composition for lithography. The method according to any one of claims 1 to 5, The coating type underlayer film forming composition for lithography in which the said coating type underlayer film forming composition contains a crosslinking | crosslinked compound further. The method according to any one of claims 1 to 5, The coating type underlayer film forming composition for lithography in which the said coating type underlayer film forming composition further contains an acid, an acid generator, or both. The method according to claim 6, The coating type underlayer film forming composition for lithography in which the said coating type underlayer film forming composition further contains an acid, an acid generator, or both. The coating type underlayer film for lithography obtained by apply | coating and baking the coating type underlayer film forming composition in any one of Claims 1-5 on a semiconductor substrate. A method of forming a photoresist pattern for use in semiconductor manufacturing, comprising the step of applying the coated underlayer film-forming composition according to any one of claims 1 to 5 onto a semiconductor substrate and firing to form a coated underlayer film. Forming a resist pattern by the process of forming this application | coating type underlayer film by the coating type underlayer film forming composition in any one of Claims 1-5, the process of forming a resist film on it, exposure and image development, on a semiconductor substrate. A method of manufacturing a semiconductor device, comprising a step, a step of etching the coating type underlayer film by a resist pattern, and a step of processing the semiconductor substrate by the patterned coating type underlayer film. The process of forming this application | coating type underlayer film by the coating type underlayer film forming composition in any one of Claims 1-5, the process of forming a hard mask on it, Furthermore, the process of forming a resist film on it, The process of forming a resist pattern by exposure and development, the process of etching a hard mask by a resist pattern, the process of etching this application underlayer film by a patterned hard mask, and the semiconductor substrate by a patterned application underlayer film A method for manufacturing a semiconductor device, comprising the step of processing a metal.